Colloid and nanosized catalysts in organic synthesis: XVII. Reductive amination of carbonitriles in the presence of supported nickel nanoparticles

Article abstract of DOI:10.1134/S1070363217110068

Reductive amination of carbonitriles catalyzed by nickel nanoparticles applied onto a solid support in a plug flow reactor in the gas phase or the gas–liquid–solid catalyst system occurs at atmospheric pressure of hydrogen affording the nonsymmetrical secondary or tertiary amines. The effect of the support type on the target product yield and conversion of the substrate has been studied.

Full text of DOI:10.1134/S1070363217110068

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 11, pp. 2546–2551. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Yu.V. Popov, V.M. Mokhov, S.E. Latyshova, A.O. Panov, P.M. Shirkhanyan, 2017, published in Zhurnal Obshchei Khimii, 2017,
Vol. 87, No. 11, pp. 1804–1809.
Colloid and Nanosized Catalysts in Organic Synthesis:
1
XVII. Reductive Amination of Carbonitriles
in the Presence of Supported Nickel Nanoparticles
Yu. V. Popov*, V. M. Mokhov, S. E. Latyshova, A. O. Panov, and P. M. Shirkhanyan
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
*
e-mail: tons@vstu.ru
Received May 15, 2017
Abstract―Reductive amination of carbonitriles catalyzed by nickel nanoparticles applied onto a solid support
in a plug flow reactor in the gas phase or the gas–liquid–solid catalyst system occurs at atmospheric pressure of
hydrogen affording the nonsymmetrical secondary or tertiary amines. The effect of the support type on the
target product yield and conversion of the substrate has been studied.
Keywords: catalysis, nanoparticles, nickel, nitrile, amine, reductive amination
DOI: 10.1134/S1070363217110068
Hydrogenation of carbonitriles is accompanied by
the formation of symmetrical secondary and tertiary
amines (along with primary ones), due to the inter-
action of the formed primary and secondary amines
with aldimines [2, 3]. Purposeful introduction of other
amines into the hydrogenated mixture can afford
nonsymmetrical di- and trialkylamines.
application of reductive amination of nitriles for
selective synthesis of imines catalyzed by Ru-based
metal complex catalyst has been studied; the products
yield was up to 90% at the nitriles conversion up to
99% [7]. N-Alkylanilines have been prepared via
hydrogenation of aromatic nitro compounds in the
presence of nitriles catalyzed by Pd/C or Rh/C: for
instance, N-n-propylaniline has been prepared within
For example, hydrogenation of benzonitrile in the
presence of n-butylamine (catalysis by Rh/C, room
temperature, pressure 3 at, n-octane medium) has
given n-butylbenzylamine in a quantitative yield [2].
The process can be catalyzed by Pt and Cu as well
1
9 h in a quantitative yield [3].
We have earlier performed liquid-phase hydrogena-
tion of carbonitriles in the presence of primary and
secondary amines leading to the reductive amination of
the nitriles [8]. However, this process is accompanied
by the formation of substantial amount of side
products due to the low concentration of hydrogen
dissolved in the liquid phase and long reaction time
(10–16 h).
[4–6]. For example, reductive amination of nitriles
catalyzed by Pt/C has been performed in a plug flow
reactor at 105°C and hydrogen (reductant) over-
pressure 6 atm with toluene as solvent [4]. The products
yield was up to 81% at the nitriles conversion up to
9
9%. Furthermore, the preparation of alkylarylamines
It should be noted that the above-described
processes demand either increased pressure or long
reaction duration. In view of that, this study aimed to
investigate the process of formation of nonsymmetrical
secondary and tertiary amines via reductive amination
of nitriles by hydrogen at atmospheric pressure in a
plug flow reactor in the presence of nickel
nanoparticles applied on a support.
via reductive amination of nitriles in the presence of
copper catalyst formed in situ via reduction of Cu
(
OTf) has been described (45°C, 20 h, water as
2
solvent, and the dimethylamine–borane complex as the
reductant; the products yield up to 60% at the nitriles
conversion up to 78%) [6].
Various adoptions of reductive amination of nitriles
have been described in the literature. For instance, the
Active carbon (BAU-A grade) and an alumino-
silicate cracking catalyst (Ceokar-2, 1.0–1.5 mm
1
For communication XVI, see [1].
2
546

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XVII.
a) (b)
2547
(
1
13.0 nm
5
00 nm
500 nm
Fig. 1. SEM images of the catalysts surface: (a) Ni/С and (b) Ni/Ceokar-2.
0
fraction) were used as the supports. The catalysts were
prepared via impregnation of the support with an
aqueous solution of nickel(II) chloride, followed by
separation of the impregnated carrier by filtration and
reduction of nickel ions with sodium borohydride
aqueous solution, as described elsewhere [1].
the Ni /C sample. The modified Ceokar-2 sample
contained 7 wt % of nickel on the average.
To prepare various nonsymmetrical amines we
performed reductive amination of nitriles 1a–1d with
cyclic secondary amines 2a, 2b as well as of nitriles
1
a, 1c with primary amines 2c, 2d in the presence of
0
0
The catalysts surface was examined by means of
SEM. It was revealed that nickel was chaotically
distributed inside the pores of the BAU-A carbon
forming nanostructured aggregates with about 40 nm
particles (see Fig. 1a). The catalyst surface on the
average contained 2 wt % of nickel.
the Ni /C or Ni /Ceokar-2 catalyst. The reaction was
performed at atmospheric pressure and 120–240°С,
specific feeding rate of the starting nitrile and amine
–
1
–1
cat
being 0.9–3.6 mL h g
1.5–6 L h g
and that of hydrogen being
–
1
–1
cat
.
The obtained data in the yield of target products
3a–3f and conversion of nitriles 1a–1d are collected in
the Table. Basing on these data and the reference
information [2–6] we suggested the scheme of the
main reaction in the presence of the Ni /C and
Ni /Ceokar-2 catalysts (Scheme 1).
In the case of the nickel catalyst applied onto
Ceokar-2, the support surface contained larger 200–
1
000 nm agglomerates as well as smaller 80–100 nm
0
particles (Fig. 1b); however, these particles were more
uniformly distributed over the surface as compared to
0
Scheme 1.
NH2
X
HN
H2
X
R4
R4
2
a, 2b
N
N
R1
N
X
NH3
X
R3
R3
_
H2
3a 3d
R1
N
a_1d
R1
NH
H N R2
2
1
2c, 2d
H2
NH2
R2
H
R2
R1
R1
N
N
R1
N
NH3
R2
H
3e, 3f
1
2
R = Pr (1a, 3a, 3e), Bu (1b, 3b), i-Pr (1c, 3c, 3f), Ph (1d, 2d, 3f); R = Cy (2c, 3e), Ph (2d, 3f); X = –CH
–
2
O– (2a, 3a, 3b),
3
4
1
3
4
1
3
4
1
2
CH – (2b, 3c, 3d); R = H, R = Et (with R = Pr); R = H, R = Pr (with R = Bu); R = R = Me (with R = i-Pr).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

2
548
POPOV et al.
Conversion of the starting nitriles and yields of the reaction products in the presence of nickel catalysts
Reaction
product
Nitrile : amine :
Nitrile
Nitrile
Amine
Catalyst
t, °С
Selectivity, % Yield, %
Н
2
molar ratio conversion, %
0
1
a
2a
3a
Ni /C
120
120
200
120
185
200
200
150
220
240
1 : 1 : 15
1 : 2 : 20
1 : 2 : 6
93
92
82
81
89
75
100
92
83
83
48
82
82
95
88
80
38
49
63
75
45
75
67
77
78
60
38
45
52
62
0
Ni /C
0
Ni /Ceokar-2
0
1
b
2a
3b
Ni /C
1 : 2 : 20
1 : 2 : 6
0
Ni /Ceokar-2
0
1
1
1
c
2b
2b
2c
3c
3d
3e
Ni /Ceokar-2
1 : 2 : 10
1 : 2 : 12
1 : 1 : 15
1 : 1 : 5
0
d
a
Ni /Ceokar-2
0
Ni /C
0
Ni /Ceokar-2
0
1
c
2d
3f
Ni /Ceokar-2
1 : 2 : 10
The data shown in the table revealed significant
effect of the structure of the starting compounds and
their ratio as well as temperature on the conversion of
the substrates, selectivity of the target reaction, and the
yield of the reductive amination of the carbonitrile.
in 60% yield. Amine 2b underwent the reaction with
benzonitrile 1d, but the yield of the target product was
as low as 38%.
The poor selectivity of the formation of N-n-butylcyclo-
hexylamine 3e via the reaction of reductive amination
of butyronitrile 1a with primary amine 2c was due to
the side reaction of disproportionation of the latter with
the formation of dicyclohexylamine. However, the dis-
proportionation was not observed in the case of aniline.
Aniline 2d exhibited low activity in the reaction, likely
due to the low basicity, and the satisfactory yield was
attained only at heating to far above 200°С.
The yield of alkylmorpholine 3a was of 67% in the
reaction of reductive amination of nitrile 1a with
0
amine 2a catalyzed by Ni /Ceokar-2 at 200°С, whereas
the yield N-isobutylmorpholine and N-isobutylpipe-
ridine under the same conditions was less than
satisfactory. The reaction of nitrile 1c with pyrrolidine
0
2
b on Ni /Ceokar-2 afforded N-isobutylpyrrolidine 3c
Scheme 2.
NH2
H2
NH2
R1
R1
R1
N
R1
N
H
a_4c
R1
R1
R1
N
NH3
H
4
H2
H
2
R1
N
a_1d
R1
R1
NH2
NH
1
R1
HN
R1
R1
R1
R1
R3
R3
H2
R1
R1
N
R1
N
N
R1
R2
R2
NH3
3
5
a, 5b
NH2
1
2
1
2
3
1
2
R = Pr (1a, 4a, 5a), Bu (1b, 4b, 5c), i-Pr (1c), Ph (1d); R = H, R = Et (with R = Pr); R = H, R = Pr (with R = Bu); R =
3
1
R = Me (with R = i-Pr).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XVII.
2549
Chromato-mass spectrometry revealed that the side
products (symmetrical di- and trialkylamines) were
formed upon hydrogenation of the starting nitriles
nonsymmetrical secondary or tertiary amines with 38–
78% yield, the nitriles conversion being 75–100%.
1
a–1d (Scheme 2).
EXPERIMENTAL
0
0
The Ni /C and Ni /Ceokar-2 catalysts were found
Chromato-mass spectral analysis was performed
using a Saturn 2100 T/GC3900 instrument (EI, 70 eV).
Quantitative GLC analysis was performed using a
active at different temperatures. For example, the
optimal temperature range of 120–150°C was found
for Ni /C, whereas further heating led to significant
decrease in the target products yield due to the catalyst
deactivation. That feature is typical for hydrogenation
of nitriles and has been discussed in the literature
0
Kristallyuks–4000M chromatograph (t 100–210°С,
s
tevap 250°С, polar column HP-5, lcol 50 m, dcol 0.32 mm,
nitrogen as carrier gas, flame ionization detector, tFID
2
50°C, acetonitrile as solvent). Scanning electron
microscopy studies were performed using a FEI Versa
D DualBeam instrument (working distance 10 mm,
[
9, 10]. However, the comparable yield of the target
0
products in the presence of Ni /Ceokar-2 was attained
at 180–240°С, the nitriles conversion being increased
with heating. For example, the yield of alkylmor-
pholine 3a at 200°С equaled 67%. It was found that
3
ETD detector of secondary electrons, CBS detector of
backscattered electrons, EDS elemental analysis method).
0
0
the Ni /Ceokar-2 catalyst remained active during 14 h
Ni /C catalyst was prepared by impregnation of
in the reaction of reductive amination of valeronitrile
BAU-A active carbon (fraction 1–15.5 mm) with
0
aqueous solution of NiCl ·6H O during a day (0.2 g of
1
b with morpholine 2a at 185°С, in contrast to Ni /C.
2
2
the nickel chloride hydrate per 0.5 g of the carbon).
The precipitate was filtered off, washed with distilled
Furthermore, according to the data collected in the
Table, the formation of the symmetrical amines 4a–4c,
a, 5b from the nitriles in the case of non-
disproportionating amines 2a, 2b, 2d could be
suppressed in the excess of the latter. For example, in
the case of the reaction of amine 2a with nitrile 1a
afforded alkylmorpholine 3a in the yield increasing
from 45 to 75% when the amine to nitrile ratio was
changed from equimolar to twofold excess of amine
water, and treated with aqueous solution of NaBH at
4
5
2
0–25°С during 20–30 min.
0
Ni /Ceokar-2 catalyst was prepared similarly,
from 2 g of the cracking catalyst Ceokar-2 (fraction 1–
1.5 mm) and 0.5 g of nickel(II) chloride hexahydrate.
Reductive amination of nitriles 1a–1f. A reduced
moist catalyst was loaded into the reactor and dried in
a hydrogen stream at 120°С just before the reaction.
The reaction was performed in a plug flow reactor at
atmospheric pressure and temperature 100–240°С. The
laboratory-scale reactor was a 12Kh18N10T steel pipe
of inner diameter 9 mm placed in an electric oven with
heating zone height 50 mm. The reactor temperature
was monitored using a thermocouple. The hydrogen
feeding was controlled using a GV-7 hydrogen generator.
2
a. In view of the possibility of the disproportionation
reaction, the 1 : 1 ratio of the reactants was optimal for
the primary amines, since both side reactions were
suppressed under these conditions.
0
In the case of the Ni /C catalyst, 15–20-fold molar
excess of hydrogen with respect to the starting nitrile
was found to be optimal. The decrease in hydrogen
excess resulted in rapid deactivation of the catalyst.
0
The relatively higher stability of the Ni /Ceokar-2
A mixture of the corresponding catalyst, nitrile, and
amine was loaded into the reactor and heated at
catalyst allowed the use of less hydrogen (6–12-fold
excess with respect to nitrile).
1
00–240°С under hydrogen flow. The reaction
The difference in the activity and stability of the
studied catalysts could be explained by the formation
of larger nickel particles in the case of the Ni /Ceokar-
course was monitored by means of chromato-mass
spectrometry.
0
Reductive amination of butyronitrile 1a. a.
2
sample, reducing the catalytic activity but enhancing
Nitrile : amine : hydrogen ratio 1 : 1 : 15, catalyst
the catalyst stability.
0
Ni /С, reaction temperature 120°С, feeding rate of a
In summary, we found that reductive amination of
carbonitriles catalyzed by nickel nanoparticles on
active carbon or aluminosilicate carrier occurred
rapidly in a plug flow reactor in a gas phase or in a gas–
liquid system at atmospheric pressure, affording
mixture of butyronitrile 1a and morpholine 2a
–
1
–1
–1
–1
3.6 mL h gcat , hydrogen feeding rate 6 L h gcat
.
Nitrile 1a conversion 93%. Yield: 45% of N-n-
butylmorpholine 3a, 31% of di-n-butylamine 4a, and
15% of tri-n-butylamine 5a.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

2
550
POPOV et al.
reaction temperature 120°С, feeding rate of a mixture
N-n-Butylmorpholine (3a). Mass spectrum, m/e
Irel, %): 143.9 (10) [M + 1], 142.7 (3) [M], 99.9 (100),
–
1
–1
(
of nitrile 1b and morpholine 2a 3.6 mL h gcat ,
–1
–1
7
0.0 (16).
hydrogen feeding rate 6 L h
gcat . Nitrile 1b
conversion 81%. Yield: 77% of N-n-pentylmorpholine
Di-n-butylamine (4a). Mass spectrum, m/e (Irel,
): 130.8 (2) [M + 2], 129.8 (15) [M + 1], 128.6 (2)
3
b and 4% of tri-n-pentylamine 5b.
%
[
M], 99.8 (8), 85.8 (100), 70 (15), 56.9 (33), 44.1 (20),
N-n-Pentylmorpholine (3b). Mass spectrum, m/e
4
3.0 (20), 41.1 (34).
(Irel, %): 158.1 (28) [M + 1], 100.1 (100), 99.2 (7), 70.1
12).
Tri-n-pentylamine (5b). Mass spectrum, m/e (Irel,
%): 228.2 (14) [M + 1], 170.0 (100), 114.0 (55), 58.0
(
Tri-n-butylamine (5a). Mass spectrum, m/e (Irel,
): 184.0 (2), 141.8 (100), 99.9 (75), 58.0 (55), 44.0
%
(
11), 41.0 (8).
(
40), 171.0 (12).
b. Nitrile : amine : hydrogen ratio 1 : 2 : 20, catalyst
0
Ni /С, reaction temperature 120°С, feeding rate of a
mixture of butyronitrile 1a and morpholine 2a
b. Nitrile : amine : hydrogen ratio 1 : 2 : 6, catalyst
0
Ni /Сeokar-2, reaction temperature 185°С, feeding rate
of a mixture of nitrile 1b and amine 2a 0.9 mL h g
hydrogen feeding rate 0.5 L h gcat . Nitrile 1b
conversion 89%. Yield: 78% of N-n-pentylmorpholine
and 9% of tri-n-pentylamine 5b.
–
1
–1
–1
–1
cat
–1
–1
cat
3
.6 mL h g , hydrogen feeding rate 6 L h g
.
,
cat
–
1
–1
Nitrile 1a conversion 92%. Yield: 75% of N-n-
butylmorpholine 3a, 11% of di-n-butylamine 4a, and
% of tri-n-butylamine 5a.
5
c. Nitrile : amine : hydrogen ratio 1 : 2 : 6, catalyst
Reductive amination of isobutyronitrile 1c. a.
0
Ni /Сeokar-2, reaction temperature 200°С, feeding rate
of a mixture of butyronitrile 1a and amine 2a
Nitrile : amine : hydrogen ratio 1 : 2 : 10, catalyst
0
Ni /Сeokar-2, reaction temperature 200°С, feeding rate
–
1
–1
–1
–1
–1
0
.9 mL h g , hydrogen feeding rate 0.5 L h gcat
.
of a mixture of nitrile 1c and pyrrolidine 2b 0.9 mL h
cat
–
1
–1
–1
Nitrile 1a conversion 82%. Yield: 67% of N-n-
butylmorpholine 3a, 12% of di-n-butylamine 4a, and
% of tri-n-butylamine 5a.
gcat , hydrogen feeding rate 0.75 L h g . Nitrile 1c
cat
conversion 75%. Yield: 60% of N-isobutylpyrrolidine
3c, 10% of N-isobutylideneisobutylamine, and 5% of
diisobutylamine 4c.
2
d. Nitrile : amine : hydrogen ratio 1 : 1 : 15, catalyst
0
Ni /С, reaction temperature 150°С, feeding rate of a
mixture of butyronitrile 1a and cyclohexylamine 2c
N-Isobutylpyrrolidine (3c). Mass spectrum, m/e
(I , %): 128.0 (19) [M + 1], 126.9 (2) [M], 84.0 (100),
rel
–
1
–1
–1
–1
cat
3
.3 mL h g , hydrogen feeding rate 6 L h g
.
42.0 (8).
cat
Nitrile 1a conversion 92%. Yield: 45% of N-n-
butylcyclohexylamine 3e, 47% of di-n-butylamine 4a,
and 10% of dicyclohexylamine.
N-Isobutylideneisobutylamine. Mass spectrum,
m/e (I , %): 127.8 (13) [M + 1], 126.7 (4) [M], 111.9
rel
(
8), 83.9 (100), 82.1 (8), 70.0 (10), 67.0 (11), 57.0
N-n-Butylcyclohexylamine (3e). Mass spectrum,
(46), 56.0 (38), 55.0 (15), 42.0 (23), 41.1 (43), 40.1 (4).
m/e (I , %): 156.8 (4) [M + 2], 155.9 (33) [M + 1],
rel
Diisobutylamine (4c). Mass spectrum, m/e (Irel,
): 129.8 (12) [M + 1], 128.9 (3) [M], 126.8 (1), 100.8
29), 99. 8 (75), 85.8 (22), 73.9 (100), 73.0 (19), 72.0
1
5
54.8 (3) [M], 111.9 (100), 83.0 (2), 70.2 (6), 57 (3),
6.1 (15), 41.1 (10).
%
(
Dicyclohexylamine. Mass spectrum, m/e (I , %):
(38), 57.9 (10), 56.9 (26), 56.0 (23), 55 (37). 46.0 (39),
43.0 (19), 41.1 (40).
rel
1
1
4
83.0 (1) [M + 2], 182.0 (11) [M + 1], 180.8 (12) [M],
52.0 (6), 138.0 (100), 82.0 (4), 56.1 (27), 44.1 (3),
1.1 (6).
b. Nitrile : amine : hydrogen ratio 1 : 2 : 10, catalyst
0
Ni /Сeokar-2, reaction temperature 240°С, feeding rate
–
1
–1
e. Nitrile : amine : hydrogen ratio 1 : 1 : 5, catalyst
of a mixture of nitrile 1c and aniline 2d 0.9 mL h g
,
cat
0
–1
–1
Ni /Сeokar-2, reaction temperature 220°С, feeding rate
of a mixture of butyronitrile 1a and cyclohexylamine
hydrogen feeding rate 0.75 L h gcat . Nitrile 1c
conversion 83%. Yield: 62% of N-isobutylaniline 3f,
19% of diisobutylamine 4c, and 2% of N-
isobutylideneisobutylamine.
–1
–1
–1
–1
cat
2
c 0.9 mL h g , hydrogen feeding rate 0.5 L h g
.
cat
Nitrile 1a conversion 83%. Yield: 52% of N-n-
butylcyclohexylamine 3e, 22%. of di-n-butylamine 4a, 9%
of tri-n-butylamine 5a, and 4% of dicyclo-hexylamine.
N-Isobutylaniline (3f). Mass spectrum, m/e (Irel,
%
[
4
): 150.8 (3) [M + 2], 149.9 (28) [M + 1], 149.0 (29)
M], 107.0 (8), 106.0 (100), 77.0 (8), 51.1 (6), 50.2 (3),
1.2 (2).
Reductive amination of valeronitrile 1b. a.
0
Nitrile : amine : hydrogen ratio 1 : 2 : 20, catalyst Ni /С,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

COLLOID AND NANOSIZED CATALYSTS IN ORGANIC SYNTHESIS: XVII.
2551
Reductive amination of benzonitrile 1d. Nitrile :
amine : hydrogen ratio 1 : 2 : 12, catalyst Ni /Сeokar-2,
j.1749-6632.1973.tb49523.x
3. Sajiki, H., Ikawa, T., and Hirota, K., Org. Lett., 2004,
vol. 6, no. 26, p. 4977. doi 10.1021/ol047871o
4. Sharma, S.K., Lynch, J., Sobolewska, A.M., Plucinski, P.,
0
reaction temperature 200°С, feeding rate of a mixture
–
1
–1
of nitrile 1d and pyrrolidine 2b 0.9 mL h gcat
,
–1
–1
Watson, R.J., and Williams, J.M.J., Catal. Sci. Technol.,
hydrogen feeding rate 1 L h gcat . Nitrile 1d
conversion 100%. Yield: 38% of N-benzylpyrrolidine
2
013, vol. 3, p. 85. doi 10.1039/c2cy20431b
5
6
. Lu, S., Wang, J., Cao, X., Li, X., and Gu, H., Chem.
Commun., 2014, vol. 50, p. 3512. doi 10.1039/C3CC48596J
. Van der Waals, D., Pettman, A., and Williams, J.M.J.,
RSC Adv., 2014, vol. 4, no. 94, p. 51845. doi 10.1039/
C4RA11193A
3
d, 38% of benzylamine, and 24% of dibenzylamine 4d.
N-Benzylpyrrolidine (3d). Mass spectrum, m/e
Irel, %): 162.0 (11) [M + 1], 160.9 (38) [M], 91.0
100), 84.0 (47), 70.0 (48), 64.9 (28), 42.0 (26).
(
(
7
. Srimani, D., Feller, M., Ben-David, Y., and Milstein, D.,
Chem. Commun., 2012, vol. 48, p. 11853. doi 10.1039/
c2cc36639h
Dibenzylamine (4d). Mass spectrum, m/e (I , %):
97.9 (18) [M + 1], 197.0 (8) [M], 196.0 (25), 105.9
72), 91.0 (100), 65.0 (21).
rel
1
(
8
. Popov, Yu.V., Mokhov, V.M., and Shcherbakova, K.V.,
Russ. J. Gen. Chem., 2016, vol. 86, no. 4, p. 798. doi
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